SPD light valves have been known for more than seventy years for use in the modulation of light. Such light valves have been proposed for use in numerous applications during that time including, e.g., alphanumeric displays and television displays; filters for lamps, cameras, displays and optical fibers; and windows, sunroofs, toys, sunvisors, eyeglasses, goggles, mirrors, light pipes and the like to control the amount of light passing therethrough or reflected therefrom as the case may be. Examples of windows include, without limitation, architectural windows for commercial buildings, greenhouses and residences, windows for automotive vehicles, boats, trains, planes and spacecraft, windows for doors including peepholes, and windows for appliances such as ovens and refrigerators including compartments thereof. Light valves of the type described herein are also known, as indicated above, as suspended particle devices or SPDs.
As used herein, the term “light valve” generally describes a cell formed of two walls that are spaced apart by a small distance, with at least one wall being transparent. The walls have electrodes thereon, usually in the form of transparent, electrically conductive coatings. Optionally the electrodes on the walls may have thin transparent dielectric overcoatings thereon. The cell contains a light-modulating element (sometimes referred to as an activatable material) which may, without limitation, be either a liquid suspension of particles, or all or a portion of the entire element may comprise a plastic film in which droplets of a liquid suspension of particles are distributed.
The liquid suspension (sometimes herein referred to as a liquid light valve suspension or as a light valve suspension) comprises small particles suspended in a liquid suspending medium. In the absence of an applied electrical field, the particles in the liquid suspension assume random positions due to Brownian movement. Hence, a beam of light passing into the cell is reflected, transmitted or absorbed depending upon the cell structure, the nature and concentration of the particles and the energy content of the light. The light valve is thus relatively dark in the OFF state. However, when an electric field is applied through the liquid light valve suspension in the light valve, the particles become aligned and for many suspensions most of the light can pass through the cell. The light valve is thus relatively transparent in the ON state.
For many applications it is preferable for all or part of the activatable material, i.e., the light modulating element, to be a plastic film rather than a liquid suspension. For example, in a light valve used as a variable light transmission window, a plastic film in which droplets of liquid suspension are distributed is preferable to a liquid suspension alone because hydrostatic pressure effects, e.g., bulging associated with a high column of light suspension, can be avoided through use of a film and the risk of possible leakage can also be avoided. Another advantage of using a plastic film is that, in a plastic film, the particles are generally present only within very small droplets and, hence, do not noticeably agglomerate when the film is repeatedly activated with a voltage.
A light valve film (also sometimes herein referred to as an SPD film) as used herein means a film or sheet, or more than one thereof comprising a suspension of particles used or intended for use in an SPD light valve. Such light valve film usually comprises a discontinuous phase of a liquid comprising dispersed particles, such discontinuous phase being dispersed throughout a continuous phase enclosed within one or more rigid or flexible solid films or sheets. Cured emulsion, which may be part of a light valve film, is sometimes also referred to as a film or film layer. The light valve film may also comprise one or more additional layers such as, without limitation, a film, coating or sheet or combination thereof, which may provide the light valve film with one or more of, for example, (1) scratch resistance, (2) protection from ultraviolet radiation, (3) reflection of infrared energy, (4) electrical conductivity for transmitting an applied electric or magnetic field to the activatable material, and (5) dielectric overcoatings.
A common (but non-limiting) construction for an SPD film has five layers, namely, from one side to the other: (1) a first sheet of polyethylene terephthalate (“PET”) plastic, conveniently 5-7 mils in thickness, (2) a very thin transparent, electrically conductive coating of indium tin oxide (“ITO”), acting or capable of acting as an electrode, on said first sheet of PET, (3) a layer of cured (i.e., cross-linked) SPD emulsion, usually 2-5 mils in thickness and, (4) a second ITO coating acting or capable of acting as an electrode on (5) a second PET plastic substrate. As stated above, additional layers which provide other functions may optionally be added to the five-layer SPD film described above. Furthermore the SPD film can be laminated, for example, with transparent hot melt adhesive films and/or glass or thicker transparent plastic sheets to provide strength and rigidity and to protect various parts of the combined unit from environmental stresses which may, otherwise, damage its performance characteristics.
U.S. Pat. No. 5,409,734 exemplifies a type of non-cross-linked light valve film that is made by phase separation from a homogeneous solution. Light valve films made by cross-linking (curing) of emulsions are also known. The methods of the present invention are specifically directed to the use of the latter type of film, i.e., film comprising a layer formed by cross-linking an emulsion, and to laminated films produced thereby. See, for example, U.S. Pat. Nos. 5,463,491 and 5,463,492, and published U.S. Patent Application No. 2005/0227061 (published Oct. 13, 2005), all of which are assigned to the assignee of the present application. Various types of SPD emulsions, and methods of curing the same, are described in U.S. Pat. Nos. 6,301,040, 6,416,827, and 6,900,923 B2, all of which are assigned to the assignee of the present application. Such films and variations thereof may be cured through cross-linking brought about by exposing the films to (1) ultraviolet radiation, (2) electron beams or (3) heat. Each of the patents/patent applications and other references cited in this application are specifically incorporated herein by reference.
A variety of liquid light valve suspensions are well known in the art and such suspensions are readily formulated according to techniques well-known to one of ordinary skill therein. The term liquid light valve suspension, as noted above, when used herein means a liquid suspending medium in which a plurality of small particles are dispersed. The liquid suspending medium comprises one or more non-aqueous, electrically resistive liquids in which there is preferably dissolved at least one type of polymeric stabilizer which acts to reduce the tendency of the particles to agglomerate and to keep them dispersed and in suspension.
Liquid light valve suspensions useful in the present invention may include any of the so-called prior art liquid suspending media previously proposed for use in light valves for suspending the particles. Liquid suspending media known in the art which are useful herein include, but are not limited to, the liquid suspending media disclosed in U.S. Pat. Nos. 4,247,175, 4,407,565, 4,772,103, 5,409,734, 5,461,506, 5,463,492, and 6,936,193 B2, the disclosures of which are incorporated herein by reference. In general one or both of the suspending medium or the polymeric stabilizer typically dissolved therein is chosen so as to maintain the suspended particles in gravitational equilibrium.
The polymeric stabilizer, when employed, can be a single type of solid polymer that bonds to the surface of the particles, but which also dissolves in the non-aqueous liquid(s) which comprise the liquid suspending medium. Alternatively, there may be two or more solid polymeric stabilizers serving as a polymeric stabilizer system. For example, the particles can be coated with a first type of solid polymeric stabilizer such as nitrocellulose which, in effect, when dissolved, provides a plain surface coating for the particles, together with one or more additional types of solid polymeric stabilizer that when dissolved, bond to or associate with the first type of solid polymeric stabilizer and also dissolve in the liquid suspending medium to provide dispersion and steric protection for the particles. Also, liquid polymeric stabilizers may be used to advantage, especially in SPD light valve films, as described for example in U.S. Pat. No. 5,463,492.
Inorganic and organic particles may be used in a light valve suspension, and such particles may be either light absorbing or light reflecting in the visible portion of the electromagnetic spectrum.
Conventional SPD light valves have generally employed particles of colloidal size. As used herein the term colloidal means that the particles generally have a largest dimension averaging 1 micron or less. Preferably, most polyhalide or non-polyhalide types of particles used or intended for use in an SPD light valve suspension will have a largest dimension which averages 0.3 micron or less and more preferably averages less than one-half of the wavelength of blue light, i.e., less than 2000 Angstroms, to keep light scatter extremely low.
More specifically with regard to the present invention, for many years, SPD light valve experts have known that a light valve cell may be constructed either with or without the cell's electrodes being in direct contact with the activatable material (i.e., a liquid suspension or a film). For example, in U.S. Pat. No. 3,655,267 (Forlini), assigned to the assignee of the present invention, in Column 1, lines 34-44 the specification reads as follows: “To apply an electric field to the suspension, conductive area electrodes are provided on a pair of oppositely disposed walls of the cell, and an electric potential applied thereto. The electrodes may be thin transparent coatings on the inner sides of the front and rear walls of the cell, thereby forming an ohmic type cell wherein the electrodes are in contact with the fluid suspension. It has also been suggested to cover the electrodes with a thin layer of transparent material such as glass in order to protect the electrodes. Such thin layers of glass form dielectric layers between the electrodes and the fluid suspension, and the cells may be termed ‘capacitive cells’.” Such dielectric coatings, if used, could prevent or reduce any migration of contaminants into the fluid suspension from either the walls of the cell or from the electrodes themselves, in addition to furnishing protection from a possible arc-over short circuit between electrodes in the event too high a voltage was applied to activate the cell or an unplanned voltage spike occurred from the power supply. As used herein the term “arc-over short circuit” means a short circuit in a light valve cell which is caused or accompanied by an electrical discharge from one electrode to the other electrode of the cell when the light valve is activated by a voltage. For cells wherein a light valve film is the activatable material, an arc-over short circuit may burn the cured emulsion and/or one or both electrodes, and may cause the cured emulsion to delaminate from one or both electrodes.
Early prior art glass dielectrics, although not limited to a particular thickness, were usually glass sheets having a thickness, because of their fragility, of many mils. One mil equals 0.001 inch or about 25.4 microns and one micron equals 10,000 Angstroms. In comparison, the overcoatings of the present invention could be any effective and convenient thickness, without limitation, such as from 10 Angstroms up to 50,000 Angstroms, although thicknesses above 1,000 Angstroms in some cases may absorb too much light and thicknesses above 10,000 Angstroms may be expensive to deposit, whereas thicknesses below 10 Angstroms, while useable, may not be sufficiently uniform over a large area substrate. In general, however, overcoatings were infrequently used in the prior art when fluid suspensions were the activatable material because it requires an extra step and expense in constructing such SPD devices, and because arc-over short circuits were rarely observed when fluid suspensions were used.
At the time U.S. Pat. No. 3,655,267 was issued, i.e., Apr. 11, 1972, SPD devices used fluid suspensions as their activatable material, and films for SPD devices had not yet been invented. Therefore, at that time the adhesiveness of the dielectric overcoatings was not relevant. However, now that films are generally used as the activatable material in SPDs the situation has changed, because it is now desirable for the film (i.e., the cured emulsion) to bond strongly to the coatings with which it is in contact in order to reduce or eliminate the chance of the film layer delaminating from the coatings and their underlying substrates. The lamination of SPD films with other glass and/or plastic sheets and films has also increased the opportunity for short circuits to occur if there are no overcoatings on the electrodes because relatively high temperatures in combination with pressures higher than atmospheric pressure generally used during the lamination procedure soften the film layer of the SPD film and can cause it to ooze beyond the pre-lamination area of the film. This sometimes creates gaps between the electrodes which can enable arc-over short circuits to occur when the SPD film is activated.
Deficiencies of Prior Art SPD Films
Several benefits of using a film as the activatable material for an SPD light valve have been discussed above. However, prior art films also had some significant deficiencies. For example, in prior art films of the type known as poly(organosiloxanes), if the layer of cured emulsion therein bonds only weakly to substrates such as the indium tin oxide (“ITO”) coatings generally used as electrodes on the plastic sheets of PET, and is subjected to shear and/or other kinds of forces that could result from any of a variety of sources such as but not limited to changes in temperature or pressure, collisions or vibrations, the cured emulsion layer can easily delaminate from one or both ITO coatings, which will often destroy the appearance and proper functioning of the SPD film.
After sandwiching an uncured layer of SPD emulsion, as disclosed in U.S. Pat. No. 6,900,923 B2, comprising a matrix polymer and a substantially immiscible liquid suspension in between two ITO-coated PET sheets, the sandwiched materials are then exposed to UV radiation to cure the emulsion and form a film. If the emulsion layer is well cured, it has been observed to be bonded to the ITO-coated PET substrates, but the bond strength is, however, weaker than may be desired. For those applications utilizing an SPD device comprising such a film, which are not subject to severe environmental stresses, the adhesion of the cured emulsion to the ITO-coated PET may suffice. However, for applications that may involve severe environmental stress, greater adhesion is desirable and may in fact be required for long-term viability. If the adhesion of a cured emulsion to a substrate is insufficient, what one generally observes is a visually objectionable non-uniform area or areas in the film, which non-uniformity results from delamination of cured emulsion from the adjacent coating(s) and related substrate or substrates.
Another deficiency of prior art SPD films is that during the process of lamination (whereby the SPD film is combined in a stack with other plastic and/or glass films or sheets), when the ambient temperature is increased to a relatively high level the film layer may ooze outside its non-laminated area. Such oozing may allow a partially empty gap to form between the electrodes near the outer edges of the film, which gap may possibly contain air which may have moisture therein, any of which, i.e., the gap, air or moisture, or a combination thereof, may be responsible for electrical short circuits when the film is activated. When such short circuits occur, they are often accompanied by an electrical arc between the electrodes on opposite sides of the film layer, which sometimes causes film to delaminate, which, as stated above, can destroy the appearance and proper functioning of the SPD film.
An SPD film in which the cured emulsion adheres relatively strongly to the ITO-coated PET substrates and also has good cohesion, as in the present invention, is especially useful because such improved adhesion and cohesion make it possible to roll up such manufactured films, which facilitates the shipment of substantial quantities of manufactured SPD film to destinations all over the world, and could enable the SPD film to be used in an application such as a roll-up type of shade. Moreover, it is also important to substantially reduce, or eliminate if possible, the oozing of the film (i.e., the activatable material) during lamination and the chance of an arc-over electrical short circuit occurring between the film electrodes when the SPD is activated with a voltage.